Adducts of olefins and trichloromethane phosphonic dichloride

ABSTRACT

Adducts of trichloromethane phosphonic dichloride and olefinically unsaturated compounds having the general formula ##STR1## WHEREIN Q designates: A. (C R&#34;R&#39;&#34;--C R R&#39;) n   
       wherein R and R&#39;, which may be the same or different, each designates 
     H, alkyl or flourine; 
     R&#34; designates H, alkyl, aryl, substituted aryl, fluorine, chlorine, bromine, cyano, carbalkoxy, carboxy, acyloxy-methylene, acyloxy propylene, acetoxy, alkoxy, sulfonyl-alkyl or sulfonyl-aryl and R&#39;&#34; designates H, alkyl, fluorine, chlorine or bromine, or R and R&#34; form together a ring system, and n is an integer of from 1 to about 500; 
     B. (CH 2  CR IV  ═ CR V  CH 2 ) m   
       wherein R IV  and R V , which may be the same or different, each designates hydrogen, methyl or chlorine, and m is an integer of from 1 to about 200.

This is a continuation of application Ser. No. 235,384, filed Mar. 16,1972, now abandoned.

This invention relates to novel adducts of trichloromethane phosphonicdichloride, and to a process for their production. More particularly, itrelates to the addition of trichloromethane phosphonic dichloride toolefinically mono- and polyunsaturated compounds and to the novelphosphonic dichlorides thus produced.

Trichloromethane phosphonic dichloride contains two chlorine atoms whichare directly bound to phosphorus, and which are very reactive. It is anobject of this invention to show that, unexpectedly, under free radicalforming conditions, trichloromethane phosphonic dichloride reactsthrough chlorine of the trichloromethyl group, and not through chlorinebound to phosphorus. This could not have been foreseen, since otherhetero-atom acid halides such as sulfonylchlorides are known to addreadily onto a double bond through the chlorine atom which is bound tothe hetero-atom.

The formed adducts, which may contain additional reactive functions onthe carbon chain attached to phosphorus, depending on the olefins ontowhich trichloromethane phosphonic dichloride has been added, represent anovel class of phosphonyl halides. The direct introduction of aphosphonic dichloride function in a single step, by addition, washitherto unknown.

The adducts may be used for a variety of purposes, including thesynthesis of agricultural chemicals, flame-retarding additives,surface-active agents, extreme high pressure oil-additives, plasticizersand modifying and finishing agents for fibers and other polymers.Furthermore, the adducts obtained according to this invention may bedehydrochlorinated to give unsaturated compounds which are capable ofpolymerizing, either alone or with other monomers, yielding phosphorusand chlorine-containing polymers.

The present invention provides methods for the addition oftrichloromethane phosphonic dichloride by which compounds of the formulaCl(CR"R'" -- CR'R)_(n) CCl₂ P(O)Cl₂ are produced, in which R and R'denote hydrogen, an alkyl group having 1-6 carbon atoms or fluorine, R"may be hydrogen, alkyl having 1-12 carbon atoms, aryl, substituted aryl,fluorine, chlorine, bromine, cyano, carbalkoxy with an alkoxy group of1-12 carbon atoms, carboxyl, acyloxy-methylene, acyloxy-propylene,acetoxy, alkyloxy having 1-6 carbon atoms, sulfonyl alkyl or sulfonylaryl; and R'" may be hydrogen, alkyl having 1-6 carbon atoms, fluorine,chlorine or bromine. Furthermore R may be linked with R" to form a ring.n is an integer which may vary between 1 and about 500, depending on theparticular method which is chosen for the interaction betweentrichloromethane phosphonic dichloride and the olefin, and on the olefinitself the chemical nature of which is defined by R, R', R" and R'".

When the reaction is directed towards the production of adducts where n≧ 2, the phosphonic dichloride may also react with a mixture of two ormore olefins, provided that they conform to the definition of R, R', R"and R'".

Bis- and polyunsaturated compounds with unconjugated double bonds reactlike monoolefins, each double bond reacting independently of the other.Thus, novel adducts are obtained from polybutadiene, polyisoprene, orneoprene, which contains segments of the structure --C(Cl)R --CH(CCl₂POCl₂)--, in which R denotes either hydrogen, chlorine or methyl.

According to the processes which will be described in detailhereinafter, it is possible, by choosing the appropriate method, tocontrol the value of n of the general formula to a large degree.

Suitable olefins include ethylene, propylene, butene-1, butene-2,isobutene, octene-1, allyl acetate, allyl benzoate, diallyl phthalate,oleic acid and its methyl ester, vinyl acetate, vinyl butyrate, vinylmethyl ether, vinyl butyl ether, vinyl chloride, vinyl bromide, vinylfluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene,trifluorochloroethylene, styrene, α- or β-methyl styrene,p-chlorostyrene, p-nitrostyrene, divinyl benzene, p-vinylbenzoic acid,methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, acryloylchloride, acrylamide, methacrylonitrile, crotonitrile, allyl cyanide,maleic anhydride, dimethyl maleate, diethyl fumarate, α- and β-pinene,cyclohexene, cyclooctene, norbornene, norbornadiene, camphenyl acetate,p-tolyl vinylsulfone, 1,4-hexadiene, 1,5-hexadiene, polybutadiene,polyisoprene, neoprene or copolymers of butadiene, isoprene,dimethylbutadiene or chloroprene with other vinylic monomers such asacrylonitrile, acrylate esters, acrylic acid or styrene.

If the olefin is a conjugated diene, novel adducts of the generalformula Cl(CH₂ CR═CR'CH₂)_(n) CCl₂ POCl₂ are produced, in which R and R'denote hydrogen, methyl and chlorine, and in which n may vary betweenone and about 200, again depending on the method of reaction, which willbe described in detail hereinafter. Suitable conjugated dienes includebutadiene, isoprene, 2,3-dimethyl butadiene and chloroprene.

The olefins mentioned hereinbefore can be divided into two groups: thosewhich polymerize and those which do not polymerize under freeradical-producing conditions.

The second class of olefins give 1:1 adducts with trichloromethanephosphonic dichloride, i.e. products of the general formulaCl(CR'"R"--CR'R)CCl₂ POCl₂ are obtained under all conditions which leadto the formation of free radicals. The reaction takes place whencatalytic amounts of compounds, which decompose thermally into radicals,are added to a mixture of the olefin and trichloromethane phosphonicdichloride, and the mixture is subsequently heated to between 50° and200°, preferably to between 80° and 150° C.

Alternatively, in the absence of free radical-producing compounds, thereactants can be irradiated with light of a wave length between 3600 and2500 A, at a temperature between 0° and 150° C.

An inert solvent may be added, but it is only needed in order to assurea homogeneous solution with the catalyst.

Suitable compounds which produce radicals at an elevated temperatureinclude azo-bis-isobutyronitrile, dibenzpinacol, ammonium persulfate,dibenzoyl peroxide, tertiary butyl perbenzoate, tertiary butylhydroperoxide, cumene hydroperoxide, di-tertiary butyl peroxide anddilauroyl peroxide. The molar ratio between the olefin and thephosphonic dichloride may vary between 0.2 to 10, but is preferablyclose to one. Between 0.1 to 10 mole % of the catalyst, calculated onthe phosphonic dichloride, is needed in order to secure reasonableconversions to adduct, but 1-5 mole % is sufficient in most cases. Thereaction may be carried out either at atmospheric pressure or atpressures up to 300 atmospheres, depending on the olefin, the molarratio between olefins and the phosphonic dichloride and the reactiontemperature.

Internal olefins, when reacting under the conditions specified above,give exclusively 1:1 adducts. Olefins like propylene, butene-1 or allylacetate give also 1:1 adduct, but low telomers are simultaneouslyformed. A higher proportion of telomers, together with 1:1 adduct isobtained from ethylene, the fluoroethylenes, chlorotrifluoroethylene,vinyl esters or vinyl ethers. For the telomers obtained in this case, nvaries from 2 to about 20, depending primarily on the molar ratiobetween the olefins and trichloromethane phosphonic dichloride and onthe temperature of reaction.

If the conditions specified above are applied to the reaction betweenother polymerizable olefins and trichloromethane phosphonic dichloride,telomers are obtained for which n of the general formula varies between2 and about 500, depending among others on the nature of the olefin, themolar ratio between olefin and the phosphonic dichloride, and thereaction temperature. Other reaction parameters being equal, the lowerrange of n is obtained from styrene, butadiene and the vinyl halides andthe higher range from acrylate esters, acrylonitrile and the vinylidenehalides. Mixtures of polymerizable olefins given telomers into whichunits of two or more monomers have been incorporated.

Another class of catalysts which brings about a reaction between olefinsand trichloromethane phosphonic dichloride consists of iron metal orferrous or ferric compounds. These compounds may be either simple saltssuch as sulfates, nitrates, acetates, chlorides, bromides or oxides, orcoordination compounds such as iron phenanthroline or iron acetylacetonate, or chloro- or bromoferrates in either valency state. In mostcases, the preferred iron-containing catalyts are ferrous -- or ferricchloride, either anhydrous or hydrated, the corresponding bromides, andthe chloro- or bromoferrates which are derived from them.

The bromide-derived iron salts or complexes, or mixed chloride-bromidecomplexes perform as good as, but not better than, the more easilyavailable chloride-containing iron salts or complexes. Especiallypreferred catalysts are the two- or three valency chloroferrates. Theyare easily prepared in situ by adding any chloride which is inerttowards the reactants to an iron chloride containing solution, the mosteffective chlorides being those which have some solubility in thereaction medium.

Such chlorides include lithium chloride, ammonium chloride,methylammonium chloride, dimethyl-, trimethyl- and tetramethylammoniumchloride, butyl- and tributylammonium chloride, laurylammonium chloride,dimethyldilaurylammonium chloride and the like. Again, the correspondingbromides perform as well, but offer no special advantage. The molarratio of inert halide to iron halide may vary between 0.1 and 10,preferably between 0.5 and 6. The haloferrates formed in this way aremore soluble in the reaction medium than ferric- or ferrous halide, andallow therefore a wider choice of solvents for the reaction.

A condition for a proper catalytic activity of the iron compounds isthat they be at least partly soluble in the reaction medium. In the caseof uncharged coordination compounds of iron, such as theacetylacetonates, there is no need for an additional solvent, but wheniron salts and the iron halide complexes are used, such a solvent isfrequently needed. It has to be inert towards the reactants and thecatalyst, but has otherwise no restrictions. Suitable solvents includechloroform, methylene chloride, acetonitrile, propionitrile,dimethylformamide, dimethylacetamide, triethyl phosphate, diethyleneglycol - diethylether, diethylsulfone and sulfolane.

Generally, a small amount of solvent is sufficient to bring about ahomogeneous solution at the reaction temperature. Thus, a proportion of0.1 to 1 of solvent with respect to the combined weight of the reactantsis frequently sufficient.

The process of the invention can be carried out in more dilutesolutions, but this offers no advantage. The olefin itself can, incertain cases, dissolve the iron compound catalyst, and then a solventis not needed. This is the case for instance with unsaturated nitriles,and maleate esters. If iron metal is the sole catalyst, a solvent isneeded which is capable of solvating iron ions. Such solvents includedimethyl formamide, dimethyl acetamide, acetonitrile and triethylphosphate. In the presence of chloride ions, non-solvating solvents suchas methylene chloride or chloroform may be used.

The reaction temperature, when using iron compounds as catalyst, mayvary between 50° and 200° C, but 70°-150° C is the preferred range.

It is frequently advantageous to add a reducing agent to the ironcompound. This particular mode of execution allows the process of theinvention to be carried out at a lower temperature than in the absenceof a reducing agent, thus ensuring a more selective reaction, givingprodudts of an improved purity. Moreover, higher conversions of thereactants into the product are achieved.

Any convenient organic or inorganic reducing agent may be used, such ashydroquinone, benzaldehyde, acetone, acetophenone, isobutylaldehyde,benzoin, acetaldehyde, butyroin, 2,6-ditert. butyl-4-methylphenol,dihydroanthracene, dibenzpinacol, pyrogallol, 1- or 2-naphtol, ironmetal, copper metal, stannous chloride, soluble sulfites and the like.The reducing agents may be used either alone or in admixture, in amountsvarying between 0.1 to 10 moles with respect to the iron compound,preferably between 0.3 and 3 moles. They may be added at the start ofthe reaction or introduced gradually at reaction temperature. Sources offree radicals described in the first section, such as organic peroxidesor azo-compounds have the same effect as reducing agents, if used incombination with the iron compound catalysts, in the molar ratiosspecified hereinbefore. In this particular combination, the catalyticeffect of the iron compounds prevails, and the obtained products andtheir distribution are identical with those obtained for iron catalysisalone or in combination with a reducing agent.

A characteristic feature of the use of iron compounds as catalysts is atendency towards formation of 1:1 adducts from trichloromethanephosphonic dichloride and olefins, in cases where catalysis by theconventional sources of free radicals leads to the formation oftelomers. Many polymerizable olefins give a 1:1 adduct which may beaccompanied by telomer. With monomers such as vinyl esters,vinylchloride, vinylbromide, vinyl ethers, butadiene, isoprene orstyrene, the molar ratio between the reactants and other reactionconditions can be adjusted so as to yield either 1:1 adduct or telomersas the main product. With vinylidene chloride, acrylic esters, acrylicacid, acrylonitrile and the like, telomers always make up more than 50%of the reaction product.

Mixtures of vinylic monomers yield telomers in which two or moremonomeric units are incorporated.

A third class of catalysts constitute cuprous or cupric compounds, orcopper metal.

As in the case of iron compounds, coordination compounds as well assimple salts or oxides have a catalytic activity. The bromides andespecially the chlorides are preferred. With copper compounds it isparticularly advantageous to add an inert chloride of the same natureand in the same quantities as defined for iron and iron compounds. Itsbeneficial effect is manifest in improved yields, faster reactions, andthe virtual absence of by-products.

The solvents which can be used for reactions catalyzed by coppercompounds are the same as for iron and iron compounds. They areessential for the reaction only insofar as they bring about ahomogeneous solution.

A reducing agent or a source of free radicals can be added in catalyticquantities, and has a distinct, though for certain olefins, a lesspronounced effect that in the case of catalysis by iron compounds. Thesame reducing agents may be used as in the case of iron compounds.Again, the product distribution is not affected by these additives.

The reaction between olefins and trichloromethane phosphonic dichloride,when catalyzed by copper compounds, can be carried out at a temperaturebetween 50° and 200° C, 70°-150° C being the preferred range.

The tendency to form 1:1 adducts from olefin and trichloromethanephosphonic dichloride is still much more pronounced for catalysis bycopper compounds as compared to catalysis by iron or iron compounds.Thus, 1:1 adducts are always the main, and frequently the sole productfrom trichloromethane phosphonic dichloride and vinylic monomers orother olefins.

The following examples are given by way of illustration of theinvention, but not by way of limitation. In the examples, all degreesare in centrigrade.

EXAMPLE 1 Adducts of butene-1

5.6 g (0.1 mole)butene-1, 71 g (0.3 mole) trichloromethane phosphonicdichloride and 0.5 g tert. butyl perbenzoate were heated in 100 mlmethylene chloride in a closed ampoule and in the absence of air, during10 hours at 120°. After cooling, the ampoule was opened and its contentsdistilled. Unconverted trichloromethane phosphonic dichloride sublimedbetween 70° and 125° at 25 mm pressure. The continued distillationyielded 10.3 g 1.1,3-trichloropentane-1-phosponic dichloride, bp/0.05:64°-66°. Found Cl: 61.3%. Calc. for C₅ H₈ Cl₅ OP: 61.0%.

The adduct was quantitatively hydrolyzed to be the correspondingphosphonic acid monochloride, liberating 12.2% chlorine as chloride ionswhich was determined argentometrically. Calc: 12.2%. 5.8 g residueremained, consisting of telomers. Replacement of tert. butyl perbenzoateby ditert. butyl peroxide gave, after 10 hours heating at 125°, 13 g1,1,3-trichloro-n-pentane-1-phosphonic dichloride.

EXAMPLE 2 Telomers of butadiene and of ethylacrylate

5.4 g (0.1 mole) butadiene, 11.8 g (0.05 mole) trichloromethanephosphonic dichloride, 10 ml dry methylene chloride and 0.1 g dibenzoylperoxide were heated in a closed ampoule at 75° during 12 hours, afterthorough degassing. After the reaction, the solution was run intorapidly stirred ice-cold isopropanol. The viscous mass whichprecipitated was dissolved again in methylene chloride, reprecipitatedin isopropanol, and dried in vacuo.

In this way, 5.2 g telomer was obtained as a very viscous oil, with MW3,950 and 5.2% chloride. It thus contains an average of 69 butadieneunits per trichloromethane phosphonic dichloride unit.

The same reaction with ethylacrylate instead of butadiene yielded 10.2 gtelomer, of MW 23,100 having 0.71% Cl and containing an average of 228acrylate units per unit of telogen.

EXAMPLE 3a Adducts of vinylchloride

6.25 g (0.1 mole) vinyl chloride, 23.6 g (0.1 mole) trichloromethanephosphonic dichloride, 540 mg (2 mmole) ferric chloride hexahydrate, 412mg (3 mmole) triethylammonium chloride, and 424 mg (2 mmole) benzoinwere heated in 30 ml acetonitrile in an ampoule at 100° during 15 hours.After opening of the ampoule, and evaporating unconverted vinylchloride, the reaction product was diluted with methylene chloride,washed twice with ice-cold 1N aqueous hydrochloric acid and dried oncalcium chloride. The solvent was distilled at atmospheric pressure, andunconverted phosphonic dichloride sublimed at 25 mm and 120°. Theremainder was fractionated in vacuo, giving 8.3 g1,1,3,3-tetrachloropropane-1-phosphonic dichloride, bp/0.1: 66°-67°;containing 70.3% Cl (Calc. for C₃ H₃ Cl₆ OP: 71.0%).

Quantitative half-hydrolysis yielded 11.63% chloride ion. Calc: 11.88%.6.5 g residue, a telomer containing an average of 3.5 vinylchlorideunits remained. Benzoin could be replaced by an equivalent amount ofdibenzpinacol, with identical results. In the absence of any reducingagent, practically no adduct was obtained.

EXAMPLE 3b

11.8 g (0.05 mole) trichloromethane phosphonic dichloride, 6.25 g (0.1mole) vinyl chloride, 100 mg (1 mmole) cuprous chloride and 63 mg (1.5mmole) lithium chloride were heated in 10 ml acetonitrile in a sealedampoule, under exclusion of air, during 20 hours at 125°. Subsequenttreatment as in Example 3a afforded 11.5 g1,1,3,3-tetrachloropropane-1-phosphonic dichloride, identical in allrespects with the product obtained in Example 3a.

Cupric chloride for cuprous chloride gave identical results. Theomission of lithium chloride caused the yield to decrease to 4.8 gadduct.

An equivalent amount of cupric acetylacetate yielded, after 20 hours at125°, 3.9 g adduct. When 3 equivalents of lithium - ortetramethylammonium chloride were added, this yield rose to 8.3 g.

When the reactions were carried out in the presence of 134 mg (1 mmole)anhydrous cupric chloride, 206 mg (1.5 mmole) triethylammonium chlorideand 366 mg (1 mmole) dibenzpinacol, 12.0 g adduct was obtained after 12hours at 110°, showing an accelerating effect of the reducing agent.

EXAMPLE 4 Propylene adducts

11.8 g (0.05 mole) distilled trichloromethane phosphonic dichloride wasdissolved in 10 ml acetonitrile, in the presence of 56 mg (1 mgr-at)iron powder. The mixture was transferred to a silver-lined autoclave of100 ml capacity, purged with propylene, and pressurized with propyleneunder agitation until 4.2 g (0.1 mole) had dissolved. The autoclave wasclosed and heated at 30° under agitation during 6 hours. After cooling,unconverted propylene was released, and the contents of the autoclavefiltered, and treated as in the previous example. Fractionation of thereaction mixture afforded 8.4 g 1,1,3-trichlorobutane-1-phosphonicdichloride, bp/0.04: 55°, and 1.2 g of the 2:1 telomer,1,1,5-trichloro-3-methylhexane-1-phosphonic dichloride, bp/0.04:99°-100°.

When the reaction was repeated with the combination of 56 mg (1 mgr-at)iron powder and 162 mg (1 mmole) anhydrous ferric chloride as thecatalytic system, 6 hours heating at 30° afforded 11.3 g1,1,3-trichlorobutane-1-phosphonic dichloride and 1.3 g1,1,5-trichloro-3-methylhexane-1-phosphonic dichloride.

EXAMPLE 5 Adducts of ethylene

5.6 g (0.2 mole) ethylene, 23.6 g (0.1 mole) trichloromethane phosphonicdichloride, 162 mg (1 mmole) anhydrous ferric chloride and 366 mg (1mmole) dibenzpinacol were heated in a 100 ml silver-lined autoclave in40 ml dry methylene chloride at 120° during 14 hours. During this timethe pressure fell from 500 to 220 psi. After cooling, the reactionproduct was extracted three times with ice-cold 1N aqueous hydrochloricacid after take-up in methylene chloride and dried on calcium chloride.Evaporation at atmospheric pressure at 50° left an oil which wasdistilled in vacuo, yielding 13.7 g 1,1,3-trichloropropane-1-phosphonicdichloride, bp/4: 105°-106°. Quantitative half-hydrolysis gave 13.4%chloride ion. Calc.: 13.4%.

5.3 g unconverted trichloromethane phosphonic dichloride was recoveredand 4 g distillation residue remained. Continued distillation gave 2.5 gof the 2:1 telomer, 1,1,5-trichloropentane-1-phosphonic dichloride,bp/0.04: 70°-71°, and 0.5 g of the 3:1 telomer,1,1,7-trichloroheptane-1-phosphonic dichloride, bp/0.04: 96°-98°. Thesame reaction, in the presence of 8.6 mg (2 mmole) lithium chlorideyielded 19.2 g 1,1,3-trichloropropane-1-phosphonic dichloride. In theabsence of dibenzpinacol, practically no reaction took place.

EXAMPLE 6 Adduct of Styrene

11.8 g (0.05 mole) trichloromethane phosphonic dichloride, 7.8 g (0.075mole) styrene, 134 mg (1 mmole) anhydrous cupric chloride and 206 mgtriethylammonium chloride were brought into solution by 5 mlacetonitrile, and heated in the absence of air in a sealed ampoule at110° during 3.5 hours. After cooling and opening of the ampoule, thereaction mixture was subjected to fractionation in vacuo, through ashort Vigreux column. 9.1 g pure 1:1 adduct,1,1,3-trichloro-3-phenyl-propane-1-phosphonic dichloride was obtainedbp/0.05: 121°. Found: Cl: 50.8, Calc. for C₉ H₈ Cl₅ OP: 52.1%

The NMR spectrum was in agreement with the proposed structure. In theabsence of triethylammonium chloride, the yield was 4.3 g.

EXAMPLE 7 Adduct of Acrylonitrile

11.8 g (0.05 mole) trichloromethane phosphonic dichloride, 134 mg (1mmole) anhydrous cupric chloride and 206 mg (1.5 mmole) triethylammoniumchloride were dissolved in 5.3 g (0.1 mole) dry acrylonitrile. Thehomogeneous solution was heated in the absence of air in a sealedampoule, at 110°, for 15 hours. Fractionation as in the previousexamples afforded 9.5 g pure 1:1 adduct,1,1,3-trichloro-3-cyanopropane-1-phosphonic dichloride, bp/0.04:90°-91°. Quantitative half-hydrolysis liberated 12.3% chloride ion;Calc.: 12.3%. The NMR spectrum agreed with the structure assigned to the1:1 adduct.

EXAMPLE 8 Adducts of Butadiene

11.8 g (0.05 mole) trichloromethane phosphonic dichloride was dissolvedin 10 ml dry methylene chloride, cooled, and a cold solution of 4 gbutadiene in 10 ml methylene chloride, which also contained 134 mg (1mmole) anhydrous cupric chloride and 206 mg (1.5 mmole) triethylammoniumchloride, was added. The resulting homogeneous solution was heated inthe absence of air, in a sealed ampoule, at 100° for 8 hours. Aftercooling, the reaction product was freed from solvent, and fractionatedthrough a short Vigreux column. 9.6 g pure 1:1 adduct,1,1,5-trichloro-pent-3-ene-1-phosphonic dichloride was obtained,bp/0.05: 92°-93°. Found: Cl: 61.3%, Calc. for C₅ H₆ Cl₅ OP: 61.0%.

Quantitative half-hydrolysis liberated 12.3% chloride ion; Calc.:12.25%. The NMR spectrum was in agreement with the structure assigned tothe adduct. When cupric chloride was replaced by an equivalent quantityof ferric chloride, together with 1 mmole benzoin, 8 hours' heating at100° yielded 5.2 g 1:1 adduct and 3.2 g 2:1 telomer Cl(C₄ H₆)₂ CCl₂POCl₂, bp/0.04; 125°-126°.

EXAMPLE 9 Adduct of Methylacrylate

To 11.8 g (0.05 mole) distilled trichloromethane phosphonic dichlorideand 8.6 g (0.1 mole) methylacrylate was added a solution of 134 mg (1mmole) anhydrous cupric chloride and 206 mg (1.5 mmole) triethylammoniumchloride in 5 ml acetonitrile. The homogeneous solution was heated inthe absence of air in a sealed ampoule at 125° for 15 hours. Aftercooling, the contents of the ampoule was subjected to distillation. 12.9g 1:1 adduct, 1,1,3-trichloro-3-carbomethoxypropane-1-phosphonicdichloride was obtained, bp/0.04: 83°. Cl⁻ (by half-hydrolysis): 11.23%.Calc. for C₅ H₆ Cl₅ O₂ P: 11.01%. In the absence of triethylammoniumchloride, 3.7 g adduct was obtained.

EXAMPLE 10 Vinylidene Chloride Adducts

11.8 g (0.05 mole) distilled trichloromethane phosphonic dichloride, 134mg (1 mmole) cupric chloride, 206 mg (1.5 mmole) triethylammoniumchloride and 9.7 g (0.1 mole) vinylidene chloride were dissolved in 10ml acetonitrile and heated in a sealed ampoule in the absence of air for15 hours at 125°. After cooling, the reaction product was diluted withmethylene chloride, once extracted with ice-cold 1N hydrochloric acidand twice with ice-water, and then dried on calcium chloride.

After evaporation of the solvent, the residue was subjected todistillation.

13.3 g 1,1,3,3,3-pentachloropropane-1-phosphonic dichloride wasobtained, bp/0.04: 69°.

Chloride ion found on the basis of half-hydrolysis: 10.43%. (Calc.:10.67%).

Continued distillation yielded 0.6 g of the 2:1 telomer,1,1,3,3,5,5,5-heptachloropentane-1-phosphonic dichloride, bp/0.04:118°-121°, chloride ion found: 9.17%. (Calc.: 8.24%).

EXAMPLE 11 Chloroprene Telomer

5.9 g (0.025 mole) trichloromethane phosphonic dichloride was heated at70° for 15 hours in a sealed ampoule with 17.7 g (0.2 mole) chloroprenein 30 ml dry methylene chloride, in the presence of 136 mgazo-bis-isobutyronitrile. The mixture had been thoroughly degassedbefore sealing. After the reaction, the mixture was diluted with 100 mlmethylene chloride and then slowly run into 1 liter ice-cold rapidlystirred isopropanol, the formed precipitate was collected, washed withcold isopropanol, and immediately dried in vacuo. It was dissolved againin 100 ml methylene chloride, reprecipitated in 1 liter cold isopropanoland dried in vacuo.

9.3 g of a polymer was thus obtained which had a molecular weight of16400, and a chlorine content of 46.3%. It thus contained for everyphosphonic dichloride end group, an average of 183 chloroprene units.

EXAMPLE 12 Polybutadiene Adduct

5.4 g all-cis polybutadiene was dissolved in 100 ml dry methylenechloride which also contained 11.8 g (0.05 mole) distilledtrichloromethane phosphonic dichloride, 62 mg (1 mmole) anhydrous ferricchloride, 206 mg (1.5 mmole) triethylammonium chloride and 212 mg (1mmole) benzoin. The viscous homogeneous solution was heated in a closed,glass-lined vessel under exclusion of air, for 5 hours at 100°. Aftercooling, the reaction mixture was run slowly into 1 liter ice-cold,rapidly stirred absolute isopropanol. The formed precipitate wasfiltered, washed well with cold isopropanol under exclusion of moisture,and dried in vacuo. 10.9 g of a polybutadiene-trichloromethanephosphonic dichloride adduct was obtained, which was film-forming, andsoluble in methylene chloride, chloroform and diethylformamide, andwhich contained 46.8% Cl and 3.0% P. Films of this material were readilycross-linked by a solution of ethylene diamine in ethylacetate.

    Examples 13-23      The adducts were prepared under the conditions specified in the table,     and isolated as described in examples 3-10.   Solvent  Chloride Reducing            Molar (20 ml Catalyst Added agent  PRODUCT  Boil- Ratio per 0.1     (mole (mole (moles  Cl(CR.sup.III R.sup.IICRR.sup.I) Yield % ing  Calc.     Olefin: mole % On per mole per mole Temp CCl.sub.2 POCl.sub.2 Calc. on     range Found Cl.sup.- Olefin Telogen TelogenTelogen catalyst catalyst     Hrs. ° R R.sup.I R.sup.II R.sup.III telogen (mm) Cl* % %     Remarks   13. Vinyl 2 CHCl.sub.3 Fe(Acac).sub.3 **(2)  -- DBP(1)*** 15     100 H H H F 45  90-92 12.3 12.6 Without DBP, fluoride             (25)     yield nil 14. Vinylidene 2 CHCl.sub.3 Cu(Acac).sub.2 (2)  -- DBP(2) 15     125 H H F F 63 105-106 11.7 11.8 Without DBP, fluoride             (25)      yield 23% 15. Vinyl bromide 2 CHCl.sub.2 CuCl.sub.2 (2) TEAC****(2)     DPB(2) 15 100 H H H Br 78  66-67 10.6 10.35 Without DBP,     (0.05)   yield 50% 16. Chloro 2 CH.sub.2 Cl.sub.2 FeCl.sub.3 (2) TEAC(2)     Benzoin(2) 15 100 F F F Cl 43  50-52 10.2 10.4 trifluoro     (0.6) ethylene 17. cis-Butene-2 4 DMF FeCl.sub.3 6H.sub.2 O(2) LiCl(4)     Benzoin(2) 15 100 H CH.sub.3 H CH.sub.3 80  60-61 12.1 12.2 Without ben-                  (0.05)   zoin, yield                nil 18. isobutene 4 DMF     FeCl.sub.3 6H.sub.2 O(2) LiCl(4) Benzoin(2) 15 100 H H CH.sub.3 CH.sub.3     85  60-62 11.8 12.2   "              (0.04) 19. Methyl- 2 CH.sub.3 CN     CuCl.sub.2 (2) TEAC(4)  --  5 110 H H C.sub.6 H.sub.5 CH.sub.3 71     128-129  8.9 10.0 Without styrene             (0.04)   TEAC,         Yield 43% 20. Butene-1 2 CH.sub.3 CN FeCl.sub.3 (1)  -- Benzoin(2)     10  90 H H H C.sub.2 H.sub.5 55  60-62 12.2 12.2 Identified     (0.04) 21. Butene-1 2 CH.sub.3 CN FeCl.sub.2 (1)  --  -- 10  90 H H H     C.sub.2 H.sub.5 37  "   by gas 22. Butene-1 2 CH.sub.3 CN FeCl.sub.3 (1)     TEAC(2)  -- 10  90 H H H C.sub.2 H.sub.5  5  "   Chromato- 23. Butene-1     2 CH.sub.3 CN FeCl.sub.3 (1) TEAC(2) Benzoin(2) 10   90 N H N C.sub.2     H.sub.5 85  " 12.0 12.2 graphy 24. Butene-1 2 CH.sub.2 Cl.sub.2  --  --     -- 10  90 H N N C.sub.2 H.sub.5 40  " 25. Butene-1 2 CH.sub.2 Cl.sub.2     --  --  -- 10  90 H -- --  ---- -- nil   Irradiated                 with     U.V.                 light                (3600-3000     R)  The adducts were prepared under the conditions specified in the     table, and isolated as described in examples 3-10    Solvent  Chloride     Reducing        Molar (20 ml Catalyst Added agent  Product  Boil- Ratio     per 0.1 (mole (mole (moles Cl(CH.sub.2 CR.sup.IV :CR.sup.V CH.sub.2)     Yield % ing Found Calc. Olefin: mole % On per mole per mole Temp.     CCl.sub.2 POCl.sub.2 calc. on range Cl.sup.- C Olefin Telogen Telogen)     Telogen catalyst) catalyst) Hrs. ° R.sup.IV R.sup.V telogen (min) %      %        26. Isoprene 2 CH.sub.2 Cl.sub.2 CuCl.sub.2 (2) TEAC -- 5 110     CH.sub.3 H 88 105-106 11.0 17.7            (0.05) 27. Chloropreno 2     CH.sub.2 Cl.sub.2 CuCl(2) TEAC (1.5) -- 5 110 Cl H 90 113-115 11.3 11.0               (0.05) 28. 2,3-Dimethyl 2 CH.sub.2 Cl.sub.2 CuCl(2) TEAC (3)     -- 5 100 CH.sub.3 CH.sub.3 65 113-16 10.5 11.2 butadiene     *Chloride ion liberated after quantitative half -- hydrolysis to     phosphonic acid monochloride.     **Acac =  Acetyl acetonate.     ***DBP = Dibenzpinacol.     ****TEAC = Triethylammonium chloride.

We claim:
 1. Compounds having the general formula ##STR2## wherein R andR' may be the same or different and are each selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl and fluorine; R" is selected fromthe group consisting of hydrogen, C₁ to C₁₂ alkyl, fluorine, bromine,chlorine, phenyl and substituted phenyl in which the substituent isselected from the group consisting of chlorine, a vinyl group, nitro andcarboxy; R'" is selected from the group consisting of hydrogen, C₁ toC₆, alkyl fluorine, chlorine, bromine, or R and R" together define aring selected from the group consisting of a cyclohexane ring, acyclooctane ring, a norbornane ring, a norbornanone ring, a2,6,6-trimethylbicyclo[3.1.1]heptane ring and a succinic anhydride ring;and n is an integer from 1 to about
 500. 2.1,1,3-trichloro-n-pentane-1-phosphonic dichloride. 3.1,1,3,3-tetrachloropropane-1-phosphonic dichloride. 4.1,1,3-trichloropropane-1-phosphonic chloride. 5.1,1,3-trichloro-3-phenylpropane-1-phosphonic dichloride. 6.1,1,3,3,3-pentachloropropane-1-phosphonic dichloride. 7.1,1,3-trichloro-3-bromopropane-1-phosphonic dichloride. 8.1,1,3-trichloro-3-fluoropropane-1-phosphonic dichloride. 9.1,1,3-trichloro-3,3-difluoropropane-1-phosphonic dichloride. 10.1,1,3-trichloro-n-butane-1-phosphonic dichloride. 11.1,1,3-trichlorobutane-1-phosphonic dichloride. 12.1,1,3-trichloro-3-methylbutane-1-phosphonic dichloride. 13.1,1,3-trichloro-3-phenylbutane-1-phosphonic dichloride. 14.1,1,3,3-tetrachloro-2,2,3-trifluoropropane-1-phosphonic dichloride. 15.1,1,5-trichloropentane-1-phosphonic dichloride. 16.1,1,3,3,5,5,5-heptachloropentane-1-phosphonic dichloride.
 17. Cl --CH₂-CH₂ --_(n) CCl₂ -POCl₂, where n is an integer of 1 to
 50. 18.Cl--CHClCH₂ --_(n) CCl₂ POCl₂ in which n = 2 to
 10. 19. b1,1,7-trichloroheptane-1-phosphonic dichloride.